Method of coating articles of food and product obtained thereby



June 24 1958 1 uswaou 0F coA 'fi ATTEN AL ARTICLES OF FOOD AND PRODUCT OBTAINED THEREBY Filed June 17, 1957 fou A,

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n U m 0H m w KR 5 0 ea W H r m H United States Patent ice METHOD OF COATING ARTICLES OF FOOD AND PRODUCT OBTAINED "IHEREBY' Lorraine E. Patten and Harold "C; Kelly, 'Midland, Mien, assignors to The Dow Chemical Company, -Midland, Mich, a corporation of Delaware I Application June 17, 1957, Serial No. 665,987 9 Claims. (Cl. 99-166) f This invention has reference to the use of'coating compositions comprising vinyl chloride polymers which are especially suited forenveloping certain articles of food, particularly meat and meat products, in tightly adhering protective coatings which may readily be stripped or peeled from the article. More particularly, it is concerned with the employment of such a coating composition as is applied from the molten condition of the type or variety that are frequently referred to and characterized as being hot melts. The invention has specific reference to a method for coating food articles with such compositions and to coated articles thereby obtained.

It would be advantageous to provide certain articles of food, particularly meat and meat products, with tough closely conforming coatings which have protective and preservative value and which could be readily removed by clean and eilicient stripping orpeeling'operations.

It would be additionally beneficial for such a coating to be imbued with other desirable characteristics, including flexibility at temperatures which are commonly encountered in refrigerators and food freezers;transparency and attractive appearance (even when the coated article is in a hard frozen condition at relatively low temperatures) relatively high impermeability to gases water and other common vapors to minimize or prevent the appearance of oxidation, dehydration or contamination in the coated foodstuff; and, as a primary requirement, absolute non-toxicity; i. e., freedom from anytendency to transfer harmful materials to the foodstuff. It would be highly desirable for such coatings to be obtainable fromreadily available and inexpensivematerials andfto be utilizable in a convenient and economic manner. I

These and other desirable advantages and benefits may be derived in the practice of the present invention which utilizes a vinyl chloride. polymer coating composition that is comprised essentially of between about 12 and 25, and preferably between about .18 and 22, percent by weight (based on the weight of .the composition) of a film-forming vinyl chloride polymer, particularly polyvinyl chloride; between about and 15 percent byweight of an epoxy typeplasticizer, preferably an epoxidized natural glyceride of unsaturated fatty acids such as the 2,840,475 Patented June 24, 1958 2 vention in any desired manner to articles which may be at any temperature beneath that of the hot melt. The hot melt itself is, in general, a viscous, transparent, slightly yellow solution having relatively rubberycharacteristics. The coating derived from the composition also exhibits analogous, relatively rubbery properties.

-, Advantageously, particularly when fresh meat ormeat epoxidized vegetable oils from soybeans of the ester type that are obtained commercially under the trade designation Paraplex G62 and .Paraplex G (or equivalent epoxidized vegetable oils containing say, from 14 to 24 carbon atoms in, its molecule) and 3-(2-xenoxyl)-l,2- 7

products are involved, the coating composition may be applied by a method which comprises freezing the article, or at least the. surface of'an article of food to be coated;

and coating the frozen article with the molten composi tion. Such a method is beneficial in that the surface of the article being coated, particularly meats and the like is less likely to attain discoloring temperatures and. those causing vaporization of surface juices. While brushing, spraying, splashing and other techniques may be employed in order'to apply the coating composition to the article, it is frequently more expedient to employ dip coating techniques for this purpose, wherein the article is dipped in the molten composition to obtain the desired coating pick-up, after which his withdrawn and the applied coating composition permitted to cool and harden. Regardless of the particular technique that is utilized for application of the coating, it is important to maintain a relatively closecontrol over the temperature of the hot melt that is being applied. Generally, hot melt temperatures between about C. and 165 C. preferably of at least C., are maintained in the hot melt composition. When lower temperatures are involved, the composition tends to become too viscous to permit practical application over the de'sired articles. At temperatures much above C., the hot melt tends to degrade and darken to an intolerable extent. I

Coated articles of food, particularly meats, in accordance with the present invention, have a highly attractive and exceptionally pleasing appearance. The coating has absolute transparency over a wide temperature range, even at temperatures as low as those in the neighborhood of l5 to 20 C. and lower. This desirable feature permits a ready visual inspection and evaluation to be made of the coated foodstuff. 'The coating is not sticky,

oily, greasy or otherwise uncomfortable {to touch or handle. It adheres tightly as a thin, limpid film about the article and conforms closely to its contours, even when bony meats or fowl are involved. It is non-toxic and does not impart objectionable odors or tastes to'the food which is coated, despite the fact that when certain plasticizers are employed in the composition, such as the acetyl citrates, the hot melt may generate a very slight, yet pleasant odor. The coating is readily-peelable, cuttable or strippable in a clean and efiicient manner from the article of food over which it is provided. It does not require washing or other tedious and inconvenient procedures for its complete removal. In addition, the coating is relatively flexible at below-freezing temperatures. Thus, it resists damage due to handlingand storage of a coated article that is being maintained in a frozen condition. It has an extremely low rate of gas and water transmission, comparable to those which are found in other distinct varieties of vinyl chloride polymer type coatings. This permits the coated articles of food to be preserved in a better condition and to be less susceptible to becoming rancid or dehydrated or to develop freezer burn. In addition, the coating composition of the present invention effectively prevents the absorbtion of undesirable foreign odors and tastes in the food product.

The vinyl chloride polymer which may be employed in the. practice of the present invention may, as has, been indicated, advantageously be polyvinylchloride. If desired, however, film-forming copolyrners of vinyl chloride with vinyl acetate may also be employed which contain in the polymer molecule atleast about 85 percent by weight of vinyl chloride. The vinyl chloride polymer" that is employed should boot the grade that has a viscosity of about 2.0 "c'enti'poises, although' polymers Whose'viscosities (as determined at 120" G. with a 2L0 percent solution of the resinin ortho dichlorobenzene) are in' the range from aboutlA to 2.5 centipoises are. generally suitable.

As has(been indicated, practically any nontoxic, com-' pati'ble plasticizer for vinyl resins canbe employed in the practice ofthe present invention, providing it is not volahowever,.-an'd bear no relationship ,to'their quality or tile (practically speaking) at the temperature of application and does not impart any, disagreeable or otherwise intolerableodor or taste tothe coating ur. the coated foodstuff. Besides dioctyl phthalate and acetyl citrates, such plasticizers as 2-ethyl hexyl diphenyl phosphate, dicapryl" phthalate, di-butyl sebacate, butylphtha'lyl butyl glycollate (availableicommercially under the trade-designation Santicizer, B16) and methylphthalyl. ethyl gly- .collate (availablecommerciallyj as Santicizer Ml7) and the like may be employed. Specific acetyl citrate plasticizers which maybe employed with great advantage in the practice of the invention are .acetyl. tributyl. citrate and acetyl triethyl citrate The above-identicated Santicizers are also capable of being utilized with z great benefit. .1 t

The use of a stabilizer facilitates retention of the clear wholesomeness in any consideration other than appearance. Thus, ifit is-suitable, food"articles. which are not .in a frozen condition may he coated satisfactorily in the practiceof the presentinvention. As a matter of fact,

there maybe instances where no siguificantadvantage andlucid characteristics of the coating compositions of,

theinvention. Typical of the non-toxic stabilizers which may be employed are those (which are available commercially Sunder the trade-designations .Ferro 707K? and Ferro 760X." These, materials, upon the, basis of reason.-

a'bleinformation :and belief, are thought to be. mixtures, in aqueous emulsion, of high imoleculan weight alkyl esters of long ehain,10,to 18 {carbon atom or so fatty acids (such as octyl stearate) and'minon-proportionsof zinc or calcium, or both, salts .of the same fatty acids.

Ferro ;7O. X,. for example, which has arelatively crystalline appearance, is thought to be a mixture of octyl stearate with about 2.5 percent by weightof zinc stearate. Ferro 760)( has a partially amorphous appearance and is thought to be a mixture of octyl stearate with about 2.5 percent by weight of zinc stearate and l percent of calcium stearate o i In. preparing the vinyl chloridepolyrner. hot melt coating compositions for use in thepresent invention, care should be taken to select ,such relative proportions of the ingredients. as will. produce a coating having. optimum characteristics. Thus,;in. some cont-binationsof ingredients, a larger proportion of the vinyl chloride polymer may produce a more viscous hoty melt'than isdesirable forparcan be realized in cooling or freezingthe article before coating. This may be the case, for example, when various smoked or cured meats, fish or fowl are being coated. The normal treated appearance of such foodstuffs is acceptable .and .does; not. detract'ifrom their marketability. By way-of illustration, variousjcuts of beef and pork were, coated. by first freezing :them and thcnldip coating them with aihotxmelt at about; 155.? C. which was comprised. of .about; 20 perce'nt by we'ight of 2.0 centipoise polyvinyl-chloride about l3,percent;,by Weight of Paraplex G162; about) percent by weight of Ferro Non- Toxic 7,07,X- and thebalance acetyl tributyl citrate. After the dipping, which in each ca serequired only a few secondssand generallynwascompleted in lessthan 5 seconds, the. coatingwas allowed IOCQOlrfiHd harden. All of the coatedjarticles, as schematicallyillustrated with one of them in a perspectiveview in Figure 11 and in cross-section in Figure 2 of theaccompanying drawing, had an attractive, sparkling andpleas'ing appearance and were not objectionable to the touch. ,'Ihe,--applied coatings, Whose thicknesses averaged, between aboutjt) and 85 mils, adheredtightlyto each ,of the articles and conformed closely to. themasa very thin, envelopingfilm abouttheir various irregular contours. The coatings were of excellent clarity,

; allowingnormal and; unimpaired visual inspection of the coated articles whichretained their essential natural appearances Thecoatings were toughand would not, be come. embrittled ,at freezing temperaturesn They could be,stripped cleanly from the articles without remnants or segments thereof: adhering tothetfoodstutf. This perrnitted'the coated articles to be obtained in their normally available condition after being freed of the coating. In addition, the coating provides apparently indefinite pro tection against the f freezer, burniwh enthe articles are maintained in a. frozen condition at sin-temperature of ticular operating temperatureswhereas smaller propor mulated composition should permitapplied film thicknesses to be obtained by hot dipping techniques th at are between about 25 andi10 0 milsl and preferably between about 50 and 85 mils with fa singleimmersion andmoden ately slow withdrawal t's ay, withinjseveral seconds) of thearticle desired to bejcoatedQ iQf course, as can readily be appreciated generallyf thinner applied coatings can be obtained, if desired, especially when otherthan dip coating techniques areutilizedffor their application. As a matter offact, it may oftentimes be economically attract i e for the thickness of the applied coatings to b'einthe neighborhood 0:10:15 r'nils 5 since the hot melt compositions that menses in pas;

about 15 C. for perioids oftirne as long as two or three months or more. No l ss inweig ht of the foodstuff that is coated inaccjordance withtthe invention and stored for theiindioated periods in a frozen condition can be determined. In addition, after such extended periods of storage,eachtof themeatspwhenthawed and stripped of'the coating is found to remain in a bright red and fresh looking condition to furnish'fui'th'er evidence of the efficacy and the moisture retaining qualities of the applied vinyl chloride polynierhot mel t coatingsi l f Equivalent good results (are similarly obtainable with other fvarities of meats and' withpoultry' if care is taken to suitably plug'orlc'ov er thecavities in their dressed carcassesf"Yarious'cheeses may also be coated satisfactorily with hotineltcompositionsjsiinilar'to the foregoing. What is claimed is: l' "1 f Method forfcoating' articles of food which comprises applying to, the article, whileit is being malntained ata relatively lower temperature, a thin envelop- 3 ing film mang thickness between aboutflO'and mils of a coatingffrlorn acoiriposition in molten form and ata'temperature between about and C., said composition consistingpf between about 12 and 25 tide of the present invention are at rela'tively high teihpei'atures lduring their application, it is advantageous to coat many articles While they in a frozen condition.

sition, of a film-forming vinyl chloride polymer selected fromfthe roup consisting of'polyvinylchloride and copolyrr'iers' of vinyl chloride with vinylacetate that contain in the polymer molecule at least about 85 percent by weight of vinyl chloride, said vinyl chloride polymer having a viscosity between about 1.4 and 2.5 centipoises as determined by measurement at 120 C. of a 2.0 percent by weight solution of the resin in ortho-dichlorobenzene; about 5 to 15 percent by weight of an epoxy type plasticizer for vinyl resins; and about 60 to 75 percent by weight of a non-toxic plasticizer for vinyl resins; and subsequently cooling the applied coating on the article to a hardened condition.

2. Method for coating articles of food which comprises freezing the article of food to be coated; applying to the article, while it is being maintained at a relatively low temperature, a thin enveloping film having a thickness between about and 100 mils of a coating from a composition in molten form and at a temperature between about 130 and 165 C., said composition consisting of between about 12 and 25 percent by Weight, based on the weight of the composition, of a film-forming vinyl chloride polymer selected from the group consisting of olyvinylchloride and copolymers of vinyl chloride with vinyl acetate that contain in the polymer molecule at least about 85 percent by weight of vinyl chloride, said vinyl chloride polymer having a viscosity between about 1.4 and 2.5 centipoises as determined by measurement at 120 C. of a 2.0 percent by weight solution of the resin in ortho-dichlorobenzene; about 5 to 15 percent by weight of an epoxy type plasticizer for vinyl resins; about 0.2 to 3 percent of a non-toxic stabilizer for vinyl resins; and about 60 to 75 percent by weight of a non-toxic plasis about 2.0 centipoises as determined by measurement 7 at C. of a 2.0 percent by Weight solution of the resin in ortho-dichlorobenzene.

7. The method of claim 2, wherein the epoxy plasticizer in composition is an epoxidized natural glyceride of unsaturated fatty acids containing from 14 to 24 carbon atoms in their molecules.

8. The method of claim 2, wherein the plasticizer in said composition is acetyl tributyl citrate.

9. A coated food article as produced by the method of claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 2,563,079 Smith Aug. 7, 1951 2,577,211 Soharf Dec. 4, 1951 2,682,475 Smith June 29, 1954 2,782,175 Bruins et al. Feb. 19, 1957 2,789,101 Wilson Apr. 16, 1957 

1. METHOD FOR COATING ARTICLES OF FOOD WHICH COMPRISES APPLYING TO THE ARTICLE, WHILE IT IS BEING MAINTAINED AT A RELATIVELY LOWER TEMPERATURE, A THIN ENVELOPING FILM HAVING A THICKNESS BETWEEN ABOUT 10 AND 100 MILS OF A COATING FROM A COMPOSITION IN MOLTEN FORM AND AT A TEMPERATURE BETWEEN ABOUT 130* AND 165*C., SAID COMPOSITION CONSISTING OF BETWEEN ABOUT 12 AND 25 PERCENT BY WEIGHT, BASED ON THE WEIGHT OF THE COMPOSITION, OF A FILM-FORMING VINYL CHLORIDE POLYMER SELECTED FROM THE GROUP CONSISTING OF POLYVINYLCHLORIDE AND COPOLYMERS OF VINYL CHLORIDE WITH VINYL ACETATE THAT CONTAIN IN THE POLYMER MOLECULE AT LEAST ABOUT 85 PERCENT BY WEIGHT OF VINYL CHLORIDE, SAID VINYL CHLORIDE POLYMER HAVING A VISCOSITY BETWEEN ABOUT 1.4 AND 2.5 CENTIPOISES AS DETERMINED BY MEASUREMENT AT 120*C. OF A 2.0 PERCENT BY WEIGHT SOLUTION OF THE RESIN IN ORTHO-DICHLOROBENZENE, ABOUT 5 TO 15 PERCENT BY WEIGHT OF AN EPOXY TYPE PLASTICIZER FOR VINYL RESINS, AND ABOUT 60 TO 75 PERCENT BY WEIGHT OF A NON-TOXIC PLASTICIZER FOR VINYL RESINS, AND SUBSEQUENTLY COOLING THE APPLIED COATING ON THE ARTICLE TO A HARDENED CONDITION. 